The pH dependence studies of Raman spectra are reported for water-soluble free-base, Zn, Co and Cu tetrakis (4-sulfonatophenyl) porphine in pH 4, pH 7 and pH 13.9 aqueous solution. For free base porphine, the substantial differences are found in absorption and Raman spectra between pH 4 and pH 7 or pH 10 aqueous solutions due to the protonation at low pH. For Zn and Co porphyrins, the hydrolysis equilibrium constants are obtained by spectrophotometric titration experiments. The consistent shifts in Raman frequencies are found at high pH due to the hydrolysis. For Cu porphyrins, instead of hydrolysis the aggregation effect is detected at high pH through the absorption and Raman studies.